Oxyalkylated derivatives of fusible acetylene-phenolic resins



1955 M. DE GROOTE EI'AL 2,723,251

OXYALKYLATED DERIVATIVES OF F USIBLE ACETYLENE-PHENOLIC RESINS Filed May5, 1955 AYAVA AYAYAYA YYY .v' A 4A,A( 777' Y WWW Melvin DeGrooteBernhard Kei INVENTO BY MWMMZQW ATTORNEYS 2,723,25l Patented Nov. 8,1955 OXYALKYLATED DERIVATIVES F FUSELE ACETYLENE-PHENOLIC RESINS MelvinDe Grootc, St. Louis, and Bernhard Kaiser, Webster Groves, Mm, assignorsto Petrolite Corporation, Wilmington, DeL, a corporation of Delaware 1Application May 5, 1953, Serial No. 353,042

5 Claims. (Cl. 26ii-52) The present invention is concerned with certainnew chemical products, compounds, or compositions which have usefulapplication in various arts. This applica tion is a continuation-in-partof our application Serial No. 129,710, filed November 28, 1949,abandoned.

Our Patent 2,574,543, granted November 13, 1951, on an application filedconcurrently with said application Serial No. 129,710, describes thebreaking of petroleum emulsions by means of certain resins oxyalkylatedwith both ethylene oxide and propylene oxide in stated relativeproportions. The new products of the present application are a smallgroup of the compositions described in our said patent, whichcompositions have outstanding properties, presumably because of thespecific proportions of the three constituents, the resin, the ethyleneoxide, and the propylene oxide, from which they are prepared. 7

Our Patent, 2,560,333, granted July 10, 1951, describes certainhydrophile synthetic products which are the oxyalkylation products ofalpha, beta-alkylene 0X- ides having not more than four carbon atoms andoxyalkylation-susceptible, fusible, organic solvent-soluble,water-insoluble, phenolic resins, which resins are derived at least inpart from acetylenic hydrocarbons. The resins described as reactants forthe production of the demulsifiers of our said patent are those used inproducing the particular small class of oxyalkylated products of thepresent application.

In the products or" the present invention, the selected phenolic resinderived at least in part from acetylenic hydrocarbons so as to introducean altered acetylenic radical as the linking structure between phenolicnuclei is oxyaikylated with both ethylene oxide and propylene oxide, insuch weight proportions of the three reactants as to come approximatelywithin the area defined by points 1, 2, 3, 4 on the accompanying chart,which is a conventional representation of a 3-component systern,proportions being weight proportions of the three components. The line34 represents a propylene oxide: ethylene oxide ratio of 55.5 :44.5; theline 4-1 about 4% resin; the point 1 about 57.5% propylene oxide and thepoint 2 40% propylene oxide; and the line 23 represents 50% resin.

Products, as above described briefly, and hereinafter described indetail, are particularly effective in breaking petroleum emulsions ofthe water-in-oil type. Oil field emulsions of this type are commonlyreferred to as cut oil," roily oil, emulsified oil, etc., and whichcomprise fine droplets of naturally-occurring waters or brines dispersedin a more or less permanent state throughout the oil which constitutesthe continuous phase of the emulsion.

The new products herein described are useful as wetting, detergent andleveling agents in the laundry, textile and dyeing industries; aswetting agents and detergems in the acid washing of building stone andbrick; a's" wetting agents and Spreaders in the application of asphaltin road building and the like; as a fiotation're- I resins, to Examplesla through 68:: for examples of agent in the flotation separation ofvarious aqueous suspensions containing negatively charged particles,such as sewage, coal washing Waste water, and various trade wastes andthe like; as germicides, insecticides, emulsitying agents, as, forexample, for cosmetics, spray oils, water-repellent textile finishes, aslubricants, etc.

A variety of resins obtained from phenol and acetylene or its polymers,or from phenols, aldehydes having 1 to 8 carbon atoms and acetylene orits polymers, useful as intermediates for producing the products ofthepresent invention are known.

We refer to our Patent 2,560,333, the application for which wascope'nding our said application Serial No. 129,710, for a detaileddescription of such resins, and to Examples 1 through 24 thereof forspecific examples of phenol-acetylene suitable phenol-Q-Ca aldehyderesins for after treatment with acetylene to produce intermediates foruse in producing the products of the invention and to Examples 117through 1011 for examples of phenol-aldehyde resins subjected to aftertreatment with acetylene to produce suitable intermediates, and toExamples 10 through 5c for examples of suitable intermediates preparedby the after treatment of phenol-acetylene resins with aldehydes.

Particularly important intermediates are those illustrated in the firsthalf of column 9 of said patent, namely, those derived from acetyleneand difunctional phenols having a hydrocarbon substituent containing atleast 4 and not more than 12 carbon atoms.

With reference to such resins, it is obvious that one might use amechanical mixture of two difierent resins, or one might employ mixturesof phenolic reactants or acetylenic reactants to produce a resin usefulas an in termediate for producing the products of the present invention.

The oxyalkylation of resins of the kind from which the products used inthe practice of the present invention are prepared is advantageouslycatalyzed by the presence of an alkali. Useful alkaline catalystsinclude soaps, sodium acetate, sodium hydroxide, sodium methylate,caustic potash, etc. The amount of alkaline catalyst usually is between0.2% to 2%. The temperature employed may vary from room temperature toas high as 200 C. The reaction may be conducted with or withoutpressure, i. e., from zero pressure to approximately 200 or even 300pounds gauge pressure (pounds per square inch). In a general way, themethod employed is substantially the same procedure as used foroxyalkylation of other organic materials having reactive phenolicgroups.

It may be necessary to allow for the acidity of a resin in determiningthe amount of alkaline catalyst to be added in oxyalkylation. Forinstance, if a non volatile strong acid such as sulfuric acid is used tocatalyze the resinification reaction, presumably after being convertedinto a sulfonic acid, it may be necessary and is usually advantageous toadd an amount of alkali equal stoichiometrically to such acidity, andinclude added alkali over and above this amount as the alkalinecatalyst.

It is advantageous to conduct the oxyethylation or oxypropylation in thepresence of an inert solvent such as xylene, cymene, decalin, ethyleneglycol diethylether, diethyleneglycol diethyle'ther, or the like,although with many resins, the oxyalkylation proceeds satisfactorilywithout a solvent. Since xylene is cheap and may be permitted to bepresent in the final product used as a demulsifier, it is our preferenceto use xylene. This is particularly true in the manufacture of productsfrom low-stage resins, i. e., of 3 and up to and including 7 units permolecule.

If a xylene solution is used in an autoclave as hereinafter indicated,the pressure readings of course represent total pressure, that is, thecombined pressure due to xylene and also due to ethylene or propyleneoxide. Under such circumstances it may be necessary at times to usesubstantial pressures to obtain efiective results, for instance,pressures up to 300 pounds along with correspondingly high temperatures,if required.

However, even in the instance of high-melting resins, a solvent such asxylene can be eliminated in either one of two ways. After theintroduction of approximately 2 or 3 moles of ethylene oxide, forexample, per phenolic nucleus, there is a definite drop in the hardnessand melting point of the resin. At this stage, if xylene or a similarsolvent has been added, it can be eliminated by distillation (vacuumdistillation if desired) and the subsequent intermediate, beingcomparatively soft and solvent-free, can be reacted further in the usualmanner with ethylene oxide or some other suitable reactant.

Another procedure is to continue the reaction to completion with suchsolvent present and then eliminate the solvent by distillation in thecustomary manner.

Attention is directed to the fact that the resins herein described mustbe fusible or soluble in an organic solvent. Fusible resins invariablyare soluble in one or more organic solvents, such as those mentionedelsewhere herein. It is to be emphasized, however, that the organicsolvent employed to indicate or assure that the resin meets thisrequirement need not be the one used in oxyalkylation. Indeed solventswhich are susceptible to oxyalkylati'on are included in this group oforganic solvents. Examples of such solvents are alcohols andalcohol-ethers. However, where a resin is soluble in an organic solvent,there are usually available other organic solvents which are notsusceptible to oxyalkylation, useful for the oxyalkylation step. In anyevent, the organic solvent-soluble resin can be finely powdered, forinstance, to 100 to 200 mesh, and a slurry or suspension prepared inxylene or the like, and subjected to oxyalkylation. The fact that theresin is soluble in an organic solvent, or the fact that it is fusible,means that it consists of separate molecules. Phenolic resins of thetype herein specified possess reactive hydroxyl groups and areoxyalkylation susceptible.

In our application Serial No. 8,730, filed February 16, 1948, nowabandoned, in regard to phenol-aldehyde resins per se, we said asfollows:

Based on molecular weight determinations, most of the resins prepared asherein described, particularly in the absence of a secondary heatingstep, contain 3 to 6 or 7 p'henolic nuclei with approximately 4 /2 or /2nuclei as an average. More drastic conditions of resinification yieldresins of greater chain length. Such more intensive resinification is aconventional procedure and may be employed, if desired. Molecularweight, of course, is measured by any suitable procedure, particularlyby cryoscopic methods; but using the same reactants and using moredrastic conditions of resinification one usually finds that highermolecular weights are indicated by higher melting points of the resinsand a tendency to decreased solubility. See what has been said elsewhereherein in regard to a secondary step involving the heating of a resinwith or without the use of vacuum.

If such resins are given an after-treatment with acetylene, and suchtreatment, in order to meet the requisites herein stated, joins at leasttwo resin molecules together by a linkage such as the following:

then, of course, there is an increase in molecular weight of at leastdouble the previous value. Similarly, resins prepared in the manner ofthe commercial product, Koresin, (the trademark employed to describecertain resins manufactured by General Aniline and Film Corporation)such as an amyl, hexyl, or octyl Koresin, yield relatively soft or tackyresins, in which there are only 3 or 4- or possibly 5 units. Such resinscan be treated further with formaldehyde in the manner described, so asto give resins of higher molecular weights than the initial resin.Therefore without attempting to elaborate too closely, we simply desireto point out that the range of molecular weight of the various resinsherein contemplated may go anywhere from a low range resin having 3 to 6or 7 phenolic nuclei with approximately 4 to 5 nuclei as an average, upto ratios double these values or in excess thereof. In other words, aphenol-aldehyde resin may be subjected to treatment with acetylene, orinversely, a phenol-acetylene resin may be treated with an aldehyde. Themost practical procedure is simply to take any mixture of phenols andtreat it with acetylene or the equivalent, to obtain a fusible, organicsolvent-soluble resin; or, if desired, prepare a phenol-aldehyde resinand treat such resin with acetylene.

As far as the preparation of the phenol-aldehyde resins go forsubsequent after-treatment with acetylene, attention is called to thefollowing paragraph which appears in our aforementioned abandonedapplication Serial No. 8,730:

We have pointed out that either an alkaline or acid catalyst isadvantageously used in preparing the resin. A combination of catalystsis sometimes used in two stages; for instance, an alkaline catalyst issometimes employed in a first stage, followed by neutralization andaddition of a small amount of acid catalyst in a second stage. It isgenerally believed that even in the presence of an alkaline catalyst,the number of moles of aldehyde, such as formaldehyde, must be greaterthan the moles of phenol employed, in order to introduce methylol groupsin the intermediate stage. There is no indication that such groupsappear in the final resin, if prepared by the use of an acid catalyst.It is possible that such groups may appear in the finished resinsprepared solely with an alkaline catalyst; but we have never been ableto confirm this fact in an examination of a large number of resinsprepared by ourselves. Our preference, however, is to use anacid-catalyzed resin, particularly employing a formaldehyde-to-phenolratio of 0.95 to 1.20, and, as far as we have been able to determine,such resins are free from methylol groups. As a matter of fact, it isprobable that in acid-catalyzed resinifications, the methylol structuremay appear only momentarily at the very beginning of the reaction, andin all probability, is converted at once into a more complex structureduring the intermediate stage.

One procedure which can be employed in the use of a new resin to prepareproducts of the invention is to determine the hydroxyl value by theVerley-Bolsing method or its equivalent. The resin as such, or in theform of a solution, as described, was then treated with a mixture ofethylene oxide and propylene oxide in presence of 0.5% to 2% of sodiummethylate as a catalyst in step-wise fashion. The ratios of propyleneoxide and ethylene oxide employed correspond to the ratios in thelimiting points on the triangular graph in the accompanying drawing, towit, 1, 2, 3, 4. Our preference is to use the propylene oxide and thenthe ethylene oxide, although useful products are obtained by usingethylene oxide and then propylene oxide or by carrying out theoxyalkylation with the use of the two oxides at the same time.

Attention is directed to the fact that in the subsequent examplesreference is made to the step-wise addition of the alkylene oxide, suchas ethylene oxide. It is understood, of course, there is no objection tothe continuous addition of alkylene oxide until the desired stage ofreaction is reached. In fact, there may be less of a hazard involved andit is often advantageous to add the alkylene oxide, or mixture, slowlyin a continuous stream and in such amount as to avoid exceeding thehigher pressures noted in the various examples or elsewhere.

It may be well to emphasize the fact that some resins are comparativelysoft or pitch-like at ordinary tempera tures. Such resins becomecomparatively fluid at 110 to 165 C., as a rule, and thus can be readilyoxyalkylated, without the use of a solvent.

Ordinarily, the oxyalkylation is carried out in autoclaves provided withagitators or stirring devices. We have found that the speed of theagitation markedly influences the time reaction. In some cases, thechange from slow speed agitation, for example, in a laboratoryautoclave, with a stirrer operating at a speed of 60 to 200 R. P. M., tohigh speed agitation with the stirrer operating at 250 to 350 R. P. M.,reduces the time required for oxyalkylation by one-half to two-thirds.Frequently xylene-soluble products which give insoluble products byprocedures employing comparatively slow speed agitation, give suitablehydrophile products when produced by similar procedure, but with highspeed agitation, as a result, we believe, of the reduction in the timerequired, with consequent elimination or curtailment of opportunity forcuring or etherization. Even if the formation of an insoluble product isnot involved, it is frequently advantageous to speed up the reaction,thereby reducing production time, by increasing agitating speed. Inlarge scale operations, we have demonstrated that economicalmanufacturing results from continuous oxyalkylation, i. e., an operationin which the alkylene oxide is continuously fed to the reaction vessel,with high speed agitation, i. e., an agitator operating at 250 to 350 R.P. M. Continuous oxyalkylation, other conditions being the same, is morerapid than batch oxyalkylation, but the latter is ordinarily moreconvenient for laboratory operation.

In the continuous addition of ethylene oxide we have employed either acylinder of ethylene oxide without added nitrogen, provided that thepressure of the ethylene oxide was sufficiently great to pass into theautoclave, or we have used an arrangement, which, in essence, was theequivalent of an ethylene oxide cylinder with a means for injectingnitrogen so as to force the ethylene oxide in the manner of an ordinaryseltzer bottle, combined with the means for either weighting thecylinder or measuring the ethylene oxide used volumetrically. In thecase of propylene oxide we invariably used nitrogen pressure to causethe oxide to move into the autoclave.

Such procedure and arrangement for injecting liquids is,- of course,conventional. In adding ethylene oxide or propylene oxide continuously,there is one precaution which must be taken at all times. The additionof the oxide must stop immediately if there is any indication thatreaction is stopped, or, obviously, if reaction is not started at thebeginning of the reaction period. Since the addition of ethylene oxideis invariably an exothermic reaction, whether or not reaction has takenplace, can be judged in the usual'manner by observing (a) Temperaturerise or drop, it any; and (b) Amount of cooling water or other meansrequired to dissipate heat of reaction;

thus, if there is a temperature drop without the use of cooling water orequivalent, or if there is no rise in temperature without using coolingwater control, careful investigation should be made.

The resins employed are prepared in the manner described in variousexamples of our said Patent 2,560,333. Instead of being prepared on alaboratory scale, they were prepared in to lS-gallonelectro-vapor-heated synthetic resin pilot plant reactors, asmanufactured by the Blaw-Knox Company, Pittsburgh, Pennsylvania, andcompletely described in their Bulletin No. 2087, issued in 1947, withspecific reference to Specification No. 7l3965.

In preparing the derivatives we have used the following procedurethroughout. Prepare the resins with a certain amountv of solvent, suchas xylene, present purely as a convenience. We have treated the resinswith propylene oxide and ethylene oxide in three different ways:

(a) Add the ethylene oxide first and then the propylene oxide;

(17) Add the propylene oxide first and then the ethylene oxide; and

(c) Use a mixture of propylene oxide and ethylene oxide, and make asingle addition.

in each case we have used an alkaline catalyst equivalent toapproximately one-half per cent to 1% of the total reaction mass in thefinal stage, or equivalent to onefourth per cent of alkaline catalystbased on final compound.

A number of resins were employed from a group of seven resins obtainedby the action of acetylene on the following seven phenols:

. ?ara-secondary butylphenol Para-tertiary amylphenol Para-phenylphenolPara-octylphenol Mixed paraand ortho propylphenol Cardanol Side-chainhydrogenated cardanol The relative proportions of the materials arethose indicated by the point circled and of the point 2 on theconventional triangular chart or graph of the attached figure. In thischart each vertex represents of the material indicated, i. e., aphenolic resin, ethylene oxide, or propylene oxide. Points in the arearepresent composition indicated in the usual manner.

Our exploration of products containing various proportions of the threeconstituents revealed that the most effective compositions from thestandpoint of demulsification and, we believe, for other purposes, werefound within three relatively restricted areas, of which one is the area1,2, 3, 4, the products represented by which are the subject matter ofthis invention While the products represented by the other two are thesubject matter of other applications filed concurrently herewith.

We prepared a series of five ditferent phenol-acetylene resins bytreating with acetylene the first five phenols in the list above, i. e.,para-secondary butylphenol, paratertiary amylphenol, para-phenylphenol,para-octylphenol, and mixed paraand ortho-propylphenol, and oxyalkylatedthem in one series in the proportions of 10 grams of resin to 100 gramsof ethylene oxide to grams of pro pylene oxide, using 250 grams ofxylene as a solvent and 1 gram of flake caustic soda as catalyst and inanother series in the proportions of 50 grams of resin to 10 grams ofethylene oxide to 40 grams of propylene oxide, with 100 grams of xyleneas a solvent and 0.5 gram of flake caustic soda as catalyst. Theoxyalkylation of each of the resins was carried out in three difierentWays:

(a) Adding-all the ethylene oxide first and then the propylene oxide;

(b) Adding the propylene oxide first and then the ethylene oxide;

(c) Mixing the two oxides and adding them simultaneously.

We have prepared also a number of similar derivatives in which thepreviously mentioned seven resins prepared from a selected phenol andacetylene were given an after-treatment with an aldehyde so as toproduce a more complex resin in which there was present more than onetype of linking unit, i. e., one derived from acetylene and one derivedfrom an aldehyde. The same applies to some resins which were prepared ina reverse manner, in which the phenol-aldehyde resin was subjected toaftertreatment with acetylene.

Resins derived exclusively from phenols and formaldehyde, react the sameway in the ethylene oxide-propylene oxide treatment as do resins derivedexclusively from comparable phenols and acetylene. It follows obviouslythat such resins in which the mixed groupings appear, i. e.,

both acetylene groupings and aldehyde groupings, must fall Within thesame limiting characteristics and this mixed type resin does actsubstantially the same and is susceptible to the same treatment as faras oxyalkylation goes, with the same results as the phenol-acetyleneresins.

We again desire to point out that the amount of alkaline catalyst usedis not critical. This is true whether the catalyst be caustic soda,caustic potash, sodium methylate, or any other suitable catalyst. Theamount which we regularly employed has varied from 1%, based on theresin alone, to 1% based on the resin and oxides, although in manycases, the reaction has been speeded up by using approximately twicethis amount of caustic. We are inclined to believe that whenever theamount of caustic represents more than 2% of the reactants present,ignoring inert solvent, that there may be some tendency, to form cyclicpolymers with the alkylene oxide, although this is purely a matter ofspeculation. For this reason, whether justified or not, we have usuallyavoided use of excess amounts of catalyst.

As we have stated, products of unusual value are produced when theircompositions are such that the three components are in proportionsrepresented by the area 1, 2, 3, 4 on the appended drawing. We haveprepared a number of derivatives which come within this area and suchderivative-s are most effective demulsifiers, and effective for otherpurposes. It is understood, of course, in each instance the compositionis based on the assumption that the percentage by weight basis is on astatistical basis, which it obviously must be, and assumes completenessof reaction.

In preparing a further series of products falling within the area 1, 2,3, 4 of the drawing, we have used a xylene solution obtained bydissolving the resin. The final product, in all instances, was adjustedto 50% xylene and 50% resin. This was purely a matter of convenience. Inthis particular series, and in fact, any other series where largeamounts of a phenol resin were employed, we have used commerciallyavailable para-tertiary butylphenol acetylene resin. The amounts ofother resins available were limited, and thus, part of the experimentswere conducted on a laboratory scale.

The resins employed in the first series of compounds which areidentified as Examples XAAl, XBBI and XFF 1, were obtained fromamylphenol acetylene resins, and which, for all practical purposes, arenothing more than the amylphenol homologues of the commerciallyavailable butyl acetylene resin. The amount of resin employed, theamount of ethylene oxide employed, and the amount of propylene oxideemployed, are given in grams in the following three examples. The weightof caustic soda employed is indicated in grams. In all these examplesall propylene oxide was added first and then all ethylene oxide.

- Ethylene Propylene Flake Ex. No. 3$; Oxide, Oxide, Caustic,

Grams Grams Grams For example, in the third series of three compoundsthe 8 same ratios were used and indentified as Examples XAA3, XBB3 andXFF3. The resin employed was prepared from acetylene andpara-phenylphenol.

A fourth series of three examples was prepared, using the same ratiosand identified as Example XAA4, XBB4 and XFF4, and prepared frompara-octylphenol.

Similarly, a fifth series was prepared from the resin obtained byreaction between mixed paraand orthopropylphenol and acetylene,designated as XAAS, XBBS and XFFS.

Likewise, a sixth series was prepared from the only presentlycommercially available phenol-the resin obtained from para-tertiarybutylphenol and acetylene Koresin as sold in the open market. This lastseries was indicated as XAA6, XBB6 and XFF 6.

In all these series the same ratios of reactants as indicated inExamples XAAl, XBBl and XFFI were used. The procedure was the same ashas been described previously in regard to oxyethylation andoxypropylation. In each instance the propylene oxide was added first andthen the ethylene oxide.

In a second series of compounds the same ratios were preserved in everyrespect, except that the ethylene oxide was-added-first and then thepropylene oxide. These series are indicated by the designations YAAl,YBBl and YFF 1, for the amylphenols, and the corresponding designationfor the others.

A third series was prepared using the same ratios except that ethyleneoxide and propylene oxide were mixed together and added simultaneously,so that oxyalkylation was a random or indifferent oxyalkylation, in thesense that no control was employed to determine which oxide combinedfirst with the resin. This third series is indicated by the prefix Zinstead of X and Y.

Examination of result-s in demulsification tests shows that the X serieswas best, the Y series very good, and the Z series good.

In the final comparison all the resins were on an equal dilution basis,of the oxyalkylated derivatives and 50% xylene.

Having thus described our invention, what We claim as new and desire tosecure by Letters Patent is: I

1. Hydrophile synthetic products; said hydrophile synthetic productsbeing oxyalkylation products which are the reaction products of (a) bothethylene oxide and alphabeta propylene oxide; and (b) anoxyalkylation-susceptible, fusible, organic solvent-soluble,water-insoluble, phenolic resin in which at least a part of the radicalslinking the phenolic nuclei are divalent radicals resulting from thereaction of an acetylenic hydrocarbon with a phenolic structure; saidresin being derived, at least in part, by reaction of a phenol with anacetylenic hydrocarbon so as to introduce an altered acetylenic radicalas the linking structure between phenolic nuclei with any remaininglinkages between phenolic nuclei being divalent radicals resulting fromphenol-aldehyde condensation and having not more than 8 carbon atoms;said oxyalkylated resin being characterized by the introduction into theresin molecule of a plurality of divalent C2H4O and Cal-I radicals, withthe proviso that the composition of said hydrophile synethetic products,based on a statistical average and assuming completeness of reaction,and calculated back to the three oxyalkylation step reactants, i. e.,resin, ethylene oxide and propylene oxide, on a percentage weight basismust fall approximately within the area defined by the points 1, 2, 3, 4of the chart in the accompanying drawing.

2. Hydrophile synthetic products; said hydrophile synthetic productsbeing oxyalkylation products which are the reaction products of (a) bothethylene oxide and alpha-beta propylene oxide; and (b) anoxyalkylationsuscepti'ole, fusible, organic solvent-soluble,water-insoluble, phenolic resin in which the radicals linking thephenolic nuclei are divalent radicals resulting from the reaction ofacetylene with a phenol; said resin being derived by reaction of aphenol with acetylene so as to introduce an altered acetylenic radicalas the linking structure between phenolic nuclei; said oxyalkylatedresin being characterized by the introduction into the resin molecule ofa plurality of divalent Cal-I40 and C3Hs0 radicals, with the provisothat the composition of said hydrophile synthetic products, based on astatistical average and assuming completeness of reaction, andcalculated back to the three oxyalkylation step reactants, i. e., resin,ethylene oxide and propylene oxide, on a percentage weight basis mustfall approximately within the area defined by the points 1, 2, 3, 4 ofthe chart in the accompanying drawing.

3. The product of claim 1, wherein the resin is derived frompara-tertiary butylphenol.

4. The product of claim 1, wherein the resin is derived frompara-tertiary amylphenol.

5. The product of claim 1, wherein the resin is derived frompara-octylphenol.

References Cited in the file of this patent UNITED STATES PATENTS OTHERREFERENCES Ellis: The Chemistry of Synthetic Resins, volume II, pages1559 to 1566, Reinhold Publishing Corporation, 1936, New York.

Zoss et aL: Industrial and Engineering Chemistry, volume 41, January1949, pages 73 to 77.

1. HYDROPHILE SYNTHETIC PRODUCTS: SAID HYDROPHILE SYNTHETIC PRODUCTSBEING OXYALKYLATION PRODUCTS WHICH ARE THE REACTION PRODUCTS OF (A) BOTHETHYLENE OXIDE AND ALPHABATA PROPYLENE OXIDE: AND (B) ANOXYALKYLATION-SUSCEPTIBLE, FUSIBLE ORGANIC SOLVENT-SOLUBLE,WATER,-INSOLUBLE, PHENOLIC RESIN IN WHICH AT LEAST A PART OF THERADICALS LINKING THE PHENOLIC NUCLEI ARE DIVALENT RADICALS RESULTINGFROM THE REACTION OF AN ACETYLENIC HYDROCARBON WITH A PHENOLICSTRUCTURE; SAID RESIN BEING DERIVED, AT LEAST IN PART, BY REACTION OF APHENOL WITH AN ACETYLENIC HYDROCARBON SO AS TO INTRODUCE AN ALTEREDACETYLENIC RADICAL AS THE LINKING STRUCTURE BETWEEN PHENOLIC NUCLEI WITHANY REMAINING LINKAGES BETWEEN PHENOLIC NUCLEI BEING